A chiral porous 3D metal-organic framework (MOF) is constructed from an enantiopure carboxylate ligand of 1,1'-biphenol, which can be utilized as adsorbent for the separation of aromatic alcohols and sulfoxides with enantioselectivity of up to 99.4%. Single-crystal X-ray diffraction analysis reveals the binding sites and host-guest interactions clearly, providing microscopic insight into the origin of the enantiosorption in the framework.